KR101282051B1 - Fluorescent Dye-Siloxane Hybrid Resin - Google Patents

Abstract

The present invention relates to a fluorescent dye siloxane hybrid resin prepared through a condensation reaction of an alkoxysilane and an organosilane to which a fluorescent dye is bonded. More specifically, a fluorescent dye comprising at least one functional group is reacted with an alkoxysilane including an organic functional group to prepare an alkoxysilane having a fluorescent dye, and an organic silanol and an organic including a thermosetting or ultraviolet curable functional group. A non-aqueous condensation reaction between alkoxysilanes produces a resin in which fluorescent dyes and siloxanes are hybridized. Fluorescent dye siloxane hybrid resin according to the present invention has excellent thermal stability, light stability, fluorescence properties and processability.

Description

Fluorescent Dye-Siloxane Hybrid Resin

The present invention relates to a fluorescent dye siloxane hybrid resin prepared through the condensation reaction of an alkoxysilane and an organosilane combined with a fluorescent dye, thereby preventing the association of the fluorescent dye and improving thermal stability, light stability, fluorescence properties and processability. .

Fluorescent dyes have been used in a wide variety of applications in light wavelength converters, lasers, color filters, solar cells and LED devices, biomedicine, and specialty coatings. Fluorescent dyes generally have better absorption coefficients, broader absorption and emission spectra, and better quantum efficiency than inorganic phosphors. It also has the advantages of high biochemical affinity and low price. On the other hand, fluorescent pigments have disadvantages in that they are less stable to heat and less stable to light than inorganic phosphors, and as the concentration of fluorescent pigments increases, the inherent properties of the fluorescent pigments cause inferior dispersion stability due to association or agglomeration. there is a problem. Associating or forming agglomerates reduces the fluorescence intensity or changes the color characteristics and reduces the light transmittance. This problem is more likely to occur in inorganic structures, polymer resins such as epoxy and silicone, and the like than when the fluorescent dye is dispersed in a liquid solvent. Recently, attempts to disperse fluorescent dyes in polymer resins and to apply them have been widely made in academia and industry. Is required. US Patent Publication No. 7041160 and US Patent Publication No. 3818371 propose a method of preventing the association of dyes and increasing dispersibility by using additives or dispersants to disperse the pigments in the matrix. However, additives and dispersants are prone to deterioration in temperature increase and problems of reducing optical properties. In addition, the Republic of Korea Patent Publication No. 2004-0074471 introduced a structure capable of photo-crosslinking in the pigment, and the Republic of Korea Patent Publication No. 2009-0031987 proposed a method of improving the stability of the pigment by introducing a cyclic structure as a partial structure. The method of controlling the structure of the pigment is to introduce a new pigment structure, it will not be able to utilize a variety of pigments previously developed.

The present invention was derived to solve the above-mentioned problems of the prior art, by chemically binding a fluorescent dye to a siloxane formed of a dense inorganic network structure, so that the fluorescent dye is surrounded by a siloxane network and protected by the association of the fluorescent dye. It is an object of the present invention to provide a fluorescent dye siloxane hybrid resin having excellent processability because it includes a functional group capable of preventing and excellent thermal stability, light stability, fluorescent properties, and thermosetting or ultraviolet curing.

In order to achieve the above object, the present invention uses a fluorescent dye siloxane hybrid resin prepared by non-hydrogen condensation reaction of an alkoxysilane and an organoalkoxysilane mixture in which fluorescent dye is bonded. Fluorescent dye siloxane hybrid refers to a fluorescent dye-bonded alkoxysilane by reacting a fluorescent dye containing at least one functional group with an alkoxysilane comprising an organic functional group, and organosilanediol and thermosetting or ultraviolet curing functional groups. It is resin manufactured through the non-aqueous condensation reaction between the organoalkoxysilane containing. Fluorescent dye siloxane hybrid resins are protected by fluorescent dyes that are chemically bonded to the siloxane and surrounded by siloxane reticulum to prevent the association of fluorescent dyes, and have excellent thermal stability, light stability, and fluorescence properties. Since it contains the functional group which can be hardened | cured, it has the outstanding processability.

Hereinafter, the present invention will be described in more detail.

The fluorescent dye siloxane hybrid resin according to the present invention is prepared through a sol-gel reaction, and in particular, the condensation reaction of the fluorescent dye-bonded alkoxysilane, organoalkoxysilane and organosilanediol is shown in Scheme 1 below. As can be done without addition of water via a non-aqueous sol-gel reaction. Unlike conventional hydrosol sol-gel reactions, non-aqueous sol-gel reactions are carried out by condensation reactions of organoalkoxysilanes and organosilanediols without addition of water, thereby improving the stability of the material and suppressing the hydroxyl groups present in the material. In addition, it is possible to prepare a fluorescent dye siloxane hybrid resin using a variety of precursors.

[Reaction Scheme 1]

M = Metal

As can be seen from the above reaction scheme, condensation reaction of the hydroxyl group of the organosilane diol as a starting material and the alkoxysilane of the alkoxysilane combined with the other monomer, organoalkoxysilane, forms an inorganic network structure. , R "to form a fluorescent dye siloxane hybrid resin modified organic group.

When preparing a fluorescent dye siloxane hybrid resin using a non-aqueous sol-gel reaction, the organoalkoxysilane is formed through a condensation reaction with a hydroxylated modified organic silane, which is preferable to lower the reaction temperature and promote the sol-gel reaction. Preferably a catalyst can be added. As a usable catalyst, metal hydroxides such as barium hydroxide, strontium hydroxide and the like can be used. The amount of catalyst to be added is not particularly limited and it is sufficient to add 0.0001-10 mol% of the monomer. The reaction is sufficient to stir at 6 to 72 hours at room temperature, and in order to promote the reaction rate and to proceed with a complete condensation reaction, induce condensation reaction at 0 to 100 ℃, preferably 40 to 80 ℃ for 1 to 24 hours Inorganic mesh structure can be formed.

In addition, by-product alcohol may be present in the fluorescent dye siloxane hybrid resin prepared through the condensation reaction, which is 0 minutes to 120 ° C. under atmospheric pressure and reduced pressure, preferably -0.1 MPa and 10 to 1 hour at 40 to 80 ° C. Can be removed by doing.

The alkoxysilane to which the fluorescent dye is bonded is prepared through the reaction of a fluorescent dye comprising at least one functional group and an alkoxysilane comprising an organic functional group. In the present invention, the alkoxysilane bonded to the fluorescent dye may be selected from the alkoxysilanes bonded to the fluorescent dye prepared in 1) to 5) below, or a mixture of two or more thereof.

1) The alkoxysilane to which the fluorescent dye is bonded is prepared through the reaction of a fluorescent dye containing a hydroxyl group with a compound of Formula 1 or a mixture thereof.

[Formula 1]

[In Formula 1, R ¹ is (C ¹ -C 20) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 8) alkyl substituted with (C 3 -C 8) cycloalkyl, (C 2 -C 20) alkenyl, (C 2 -C20) alkynyl, (C6 ~ C20) aryl, wherein R ¹ may have one or more functional groups selected from isocyanates, (C1-C20) alkoxy groups, and hydroxy groups; R ² is linear or branched (C 1 -C 7) alkyl.]

2) The alkoxysilane to which the fluorescent dye is bonded is prepared through the reaction of a fluorescent dye comprising at least one of a carboxyl group, a urethane group, and a urea group with a compound of Formula 2 or a mixture thereof.

[Formula 2]

[In Formula 2, R ³ is (C1-C20) alkyl, (C3-C8) cycloalkyl, (C3-C20) alkyl substituted with (C3-C8) cycloalkyl, (C2-C20) alkenyl, (C2 -C20) alkynyl, (C6 ~ C20) aryl, wherein R3 has an isocyanate functional group; R ² is linear or branched (C 1 -C 7) alkyl.]

3) The alkoxysilane to which the fluorescent dye is bonded is prepared through the reaction of a fluorescent dye comprising at least one amino group of primary, secondary, and tertiary compounds with a compound of Formula 3 or a mixture thereof.

(3)

[In Formula 3, R ⁴ is (C1-C20) alkyl, (C3-C8) cycloalkyl, (C3-C8) alkyl substituted with (C3-C8) cycloalkyl, (C2-C20) alkenyl, (C2 ˜C20) alkynyl, (C6 ~ C20) aryl, and R ⁴ may have one or more functional groups selected from isocyanate groups, isothiocyanate groups, epoxy groups, halide groups, carbonyl groups; R ² is linear or branched (C 1 -C 7) alkyl.]

4) The alkoxysilane to which the fluorescent dye is bonded is prepared through the reaction of a fluorescent dye containing a cyano group with a compound of Formula 4 or a mixture thereof.

[Formula 4]

[In Formula 4, R ⁵ is (C1-C20) alkyl, (C3-C8) cycloalkyl, (C3-C20) alkyl substituted with (C3-C8) cycloalkyl, (C2-C20) alkenyl, (C2 -C20) alkynyl, (C6 ~ C20) aryl, wherein R ⁵ may have one or more functional groups selected from amino, alkene, halide groups; R ² is linear or branched (C 1 -C 7) alkyl.]

5) The alkoxysilane to which the fluorescent dye is bonded is prepared through the reaction of a fluorescent dye including isothiocyanate with a compound of Formula 5 or a mixture thereof.

[Chemical Formula 5]

[In Formula 5, R ⁶ is (C1-C20) alkyl, (C3-C8) cycloalkyl, (C3-C8) alkyl substituted with (C3-C8) cycloalkyl, (C2-C20) alkenyl, (C2 ~ C20) alkynyl, (C6 ~ C20) aryl, wherein R ⁶ has an amino functional group; R ² is linear or branched (C 1 -C 7) alkyl.]

The organoalkoxysilane may be selected from a compound represented by the following formula (6) or a mixture thereof as a silane compound in which a substituted or unsubstituted organic chain and an alkoxy group are bonded.

[Formula 6]

[In Formula 6, R ⁷ is (C1-C20) alkyl, (C3-C8) cycloalkyl, (C3-C20) alkyl substituted with (C3-C8) cycloalkyl, (C2-C20) alkenyl, (C2 -C20) alkynyl, (C6 ~ C20) aryl, wherein R ⁷ may have one or more functional groups selected from acryl, methacryl, vinyl, and epoxy groups; R ² is linear or branched (C 1 -C 7) alkyl.]

More specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxy Silane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltripropoxysilane, 3-acryloxypropylmethylbis (trimethoxy) silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3- (meth) acrylic Oxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltripropoxy It may be selected from silanes or mixtures thereof, but is not necessarily limited thereto.

The organosilanediol may be selected from a compound represented by the following Formula 7 or a mixture thereof as a silane compound in which a functional group has a substituted or unsubstituted organic chain and two hydroxyl groups bonded thereto.

[Formula 7]

[In Formula 7, R ⁸ and R ⁹ are independently (C1-C20) alkyl, (C3-C8) cycloalkyl, (C3-C8) alkyl substituted with (C3-C8) cycloalkyl, (C2-C20) Alkenyl, (C2-C20) alkynyl, (C6-C20) aryl, wherein R ⁸ and R ⁹ are an acryl group, methacryl group, allyl group, halogen group, amino group, mercapto group, ether group, ester At least one functional group selected from a group, a (C1-C20) alkoxy group, a sulfone group, a nitro group, a hydroxyl group, a cyclobutene group, a carbonyl group, a carboxyl group, an alkyd group, a urethane group, a vinyl group, a nitrile group, and an epoxy group Can have]

More specifically, it may be selected from diphenylsilane diol, diisobutylsilane diol or a mixture thereof, but is not necessarily limited thereto.

To adjust the viscosity of the siloxane resin consisting of the organic oligosiloxane hybrid and may be added a solvent for the stability of the resin. The solvent that can be used is not particularly limited but is preferably an aliphatic hydrocarbon solvent such as hexane or heptane or a ketone solvent such as methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, cyclohexanone, acetone or tetrahydro. Ether solvents such as furan, isopropyl ether and propylene glycol propyl ether or acetate solvents such as ethyl acetate, butyl acetate and propylene glycol methyl ether acetate or alcohol solvents such as isopropyl alcohol and butyl alcohol or dimethylacetamide and dimethyl Amide solvents such as formamide or silicone solvents or mixtures thereof may be used.

The organic oligosiloxane hybrid has a quantum dot, an inorganic phosphor, a conjugated polymer, a surfactant, an antioxidant, and an active oxygen within a range that does not affect the effect of the present invention on the siloxane resin composed of the organic oligosiloxane hybrid to control the secondary performance. Scavengers, silica sol, oxide or nitride nanoparticles, flame retardant, metal filler, heat-resistant agent and the like.

The siloxane resin including the organic oligosiloxane hybrid prepared in the present invention may include thermal curing or photocuring when the organic functional group capable of thermal polymerization or photopolymerization is modified. When the organic oligosiloxane hybrid has a photocurable or thermosetting functional group, the monomer, photocurable or thermosetting functional group may be added or other functional groups may be mixed to control the density, free volume, adhesion to the substrate, and refractive index of the organic oligosiloxane hybrid. have.

In addition, the organic oligo oligomer prepared when the organic oligosiloxane hybrid has organic functional groups such as epoxy groups, acrylic groups, methacryl groups, vinyl groups, amino groups, and hydroxyl groups, such as epoxy groups, acrylic groups, organosilane diols, and the like. The siloxane hybrid may undergo a thermosetting or ultraviolet curing step between organic groups. The thermosetting or ultraviolet curing step can be carried out under commonly used catalysts. In addition, after thermal curing or photocuring may include a step of heat treatment at 180 ℃ or less, specifically 50 to 180 ℃, preferably 150 ℃ or less, specifically 50 to 150 ℃.

The fluorescent dye siloxane hybrid resin proposed in the present invention can be used as an optical wavelength converter, a laser, a color filter, a solar cell, and an LED device.

Fluorescent dye siloxane hybrid resin prepared by the present invention is because the fluorescent dye is chemically bonded to the siloxane is surrounded by the siloxane reticular structure to prevent the association of the fluorescent dye and excellent thermal stability, light stability, fluorescent properties It has excellent processability because it has a functional group capable of having a thermal curing or ultraviolet curing.

In addition, the fluorescent dye siloxane hybrid resin prepared according to the present invention is because the inorganic and organic components are uniformly mixed at the molecular level, it can be said that the stability of the resin is very high, the mechanical and thermal properties are very excellent and the light transmittance is excellent. In addition, since various organic groups or organic functional groups can be provided, various physical properties such as refractive index can be controlled.

The invention is illustrated by the following examples. However, these do not limit the technical scope of the present invention.

Example 1

7-amino-4-methylcoumarin (coumarin 120) and 3-isocyanatepropyltriethoxysilane were added in a 1: 1 molar volume in a 10 ml glass bottle, and the lid was closed and reacted using a magnetic stirrer at room temperature for 2 hours. The amino functional group of 7-amino-4-methylcoumarin and the isocyanate functional group of 3-isocyanatepropyltriethoxysilane were reacted to obtain an alkoxysilane to which coumarin was bound. The above coumarin-bonded alkoxysilane was added to a 200 ml flask with 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and diphenylsilanediol in a 0.001: 2: 3 molar ratio, and then barium hydroxide was used as a catalyst. 0.1 mol% of the silane was added and stirred at 80 ° C. for 4 hours to obtain a coumarin siloxane hybrid resin having blue fluorescence. An aryl sulfonium hexafluoro antimony salt was added to the synthesized coumarin siloxane hybrid resin as a photocuring catalyst to 4 wt% of the organic oligosiloxane resin and placed in a 1 mm thick mold made of plastic. It was exposed to an ultraviolet lamp of 365 nm wavelength for 1 minute. After photocuring, the mold was removed and further cured at 120 ° C. for 2 hours.

[Example 2]

2- (6-amino-3-imino-3H-xanthen-9-yl) benzoic acid methyl ester (rhodamine 123) and 3-isocyanatepropyltriethoxysilane in a 1: 1 molar volume in a 10 ml glass bottle After the lid was closed and reacted with a magnetic stirrer at room temperature for 2 hours. The alkoxysilane to which coumarin is bonded by the reaction of the amino function of 2- (6-amino-3-imino-3H-xanthen-9-yl) benzoic acid methyl ester with the isocyanate functional group of 3-isocyanatepropyltriethoxysilane Obtained. The above coumarin-bonded alkoxysilane was added to a 200 ml flask with 3-glycidoxypropyltrimethoxysilane and diphenylsilanediol in a 0.001: 2: 3 molar ratio, and then barium hydroxide was used as a catalyst to 0.1 mol% of silane. Addition and stirring for 4 hours at 80 ℃ to obtain a rhodamine siloxane hybrid resin having a green fluorescence. To the synthesized rhodamine siloxane hybrid resin was added 1 mole per equivalent of phthalic anhydride as a thermosetting catalyst, and the resin was placed in a 1 mm thick mold made of polymer coated glass. Thermal curing was performed at 200 ° C. for 2 hours for thermal curing. The mold was removed after thermosetting.

[Example 3]

Fluorescein and 3-isocyanatepropyltriethoxysilane were added in a 10 ml glass bottle at a ratio of 1: 2, and the cap was closed and reacted with a magnetic stirrer at 70 ° C. for 2 hours. The hydroxy functional group of fluorescein and the isocyanate functional group of 3-isocyanatepropyltriethoxysilane were reacted to obtain an alkoxysilane to which fluorescein was bound. The above fluorescein-bonded alkoxysilane was added to a 200 ml flask with 3-methacrylopropyltrimethoxysilane and diphenylsilanediol in a 0.001: 2: 3 molar ratio. It was added and stirred for 4 hours at 80 ℃ to obtain a fluorine siloxane hybrid resin having a green fluorescence. 1,6-hexanediol diacrylate was added to the synthesized fluorescein siloxane hybrid resin in an equivalent ratio, 2,2-dimethoxy-2-phenyl acetophenone was added to the organic oligosiloxane resin as a photocuring catalyst. The resin was placed in a 1mm thick mold made of plastic. It was exposed for 4 minutes to an ultraviolet lamp having a wavelength of 365 nm. After photocuring, the mold was removed and further cured at 120 ° C. for 2 hours.

Example 4

4- (Dicyanomethylene) -2-methyl-6- (4-dimethylaminostilyl) -4H-pyran (DCM-OH) and 3-isocyanatepropyltriethoxysilane modified with hydroxyl groups at 1: 2 mol Put in a 10ml glass bottle and closed the lid and reacted with a magnetic stirrer for 6 hours at 60 ℃. The hydroxy functional group of DCM and the isocyanate functional group of 3-isocyanatepropyltriethoxysilane were reacted to obtain an alkoxysilane to which DCM was bound. The above-mentioned DCM-alkoxyalkoxysilane was added to a 200 ml flask with vinyltrimethoxysilane and diphenylsilanediol in a 0.001: 2: 3 molar ratio, and then 0.1 mol% of barium hydroxide was added as a catalyst at 80 ° C. Stirring for 4 hours yields a DCM siloxane hybrid resin with red fluorescence. Trimethylolpropane triacrylate was added to the synthesized DCM siloxane hybrid resin in an equivalent ratio, and 4 wt% of benzoyl peroxide was added to the organic oligosiloxane resin as a photocuring catalyst, and the resin was placed in a mold having a thickness of 1 mm made of plastic. It was exposed for 4 minutes to an ultraviolet lamp having a wavelength of 365 nm. After photocuring, the mold was removed and further cured at 120 ° C. for 2 hours.

[Example 5]

2,5-diamino-3,6-dicyanopyrazine and 3-aminopropyltrimethoxysilane in a 1: 2 mole ratio were placed in a 10 ml glass bottle, covered with a lid, and reacted using a magnetic stirrer at 70 ° C. for 24 hours. I was. The cyano functional group of 2,5-diamino-3,6-dicyanopyrazine and the amino functional group of 3-aminopropyltrimethoxysilane react to form 2,5-diamino-3,6-dicyanopyrazine. An alkoxysilane was obtained. The above-mentioned alkoxysilane combined with 2,5-diamino-3,6-dicyanopyrazine was added to a 200 ml flask with a vinyltrimethoxysilane and diphenylsilanediol in a 0.001: 2: 3 molar ratio, and then oxidized with a catalyst. 0.1 mol% of barium was added to the silane and stirred at 80 ° C. for 4 hours to obtain a 2,5-diamino-3,6-dicyanopyrazine siloxane hybrid resin having green fluorescence. To the synthesized 2,5-diamino-3,6-dicyanopyrazine siloxane hybrid resin, trimethylolpropane triacrylate was added in an equivalent ratio, and 4 wt% of benzoyl peroxide was added to the organic oligosiloxane resin as a photocuring catalyst. Was placed in a 1 mm thick mold made of plastic. It was exposed for 4 minutes to an ultraviolet lamp having a wavelength of 365 nm. After photocuring, the mold was removed and further cured at 120 ° C. for 2 hours.

[Example 6]

Fluorescein 5 (6) -isothiocyanate (FITC) and 3-aminopropyltrimethoxysilane were added in a 1: 1 molar volume in a 10 ml glass bottle, capped, and reacted using a magnetic stirrer at room temperature for 4 hours. I was. The isothiocyanate functional group of FITC and the amino functional group of 3-aminopropyltrimethoxysilane were reacted to obtain an alkoxysilane to which the FITC was bound. The above-mentioned alkoxysilane bonded to FITC was added to a 200 ml flask with 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and diphenylsilanediol in a molar ratio of 0.001: 2: 3, and then barium hydroxide was used as a catalyst. After adding 0.1 mol% to the mixture, the mixture was stirred at 80 ° C. for 72 hours, propylene glycol methyl ether acetate was added thereto, and the reaction mixture was removed at -0.1 MPa and 60 ° C. for 30 minutes using a reduced pressure evaporator. Eggplants yielded FITC siloxane hybrid resins. To the synthesized FITC siloxane hybrid resin, phthalic anhydride was added to the organic oligosiloxane resin by phthalic anhydride as a thermosetting catalyst, and the resin was placed in a 1 mm thick mold made of polymer coated glass. Thermal curing was performed at 200 ° C. for 2 hours for thermal curing. The mold was removed after thermosetting.

[evaluation]

The samples obtained in Example 4 were selected and evaluated as follows.

(a) photostability

After exposing the sample to a lamp having a wavelength of 365 nm for 20 hours, the fluorescence intensity was measured using a PSI fluorescence analyzer DARSA PRO 5100.

(b) thermal stability

After the sample was placed in an oven at 600 ° C. for 600 hours, the fluorescence intensity was measured using a PSI fluorescence analyzer DARSA PRO 5100.

(c) stability of association of fluorescent dyes

Samples were prepared while increasing the concentration of fluorescent dyes, and the fluorescence intensity was measured using a fluorescence analyzer DARSA PRO 5100 of PSI.

[Table 1] Comparison of fluorescence intensity before and after heat treatment of fluorescent dye siloxane hybrid resin and control group

[Table 2] Comparison of fluorescence intensity according to the concentration of fluorescent dye siloxane hybrid resin and the fluorescent dye of the control group (comparison stability of association)

Table 1 compares the fluorescence intensity before and after heat treatment of the fluorescent dye siloxane hybrid sample and the control group according to Example 4. The control is a sample cured by mixing fluorescent dyes of the same concentration as the fluorescent dye siloxane hybrid resin with a commercial epoxy polymer. When the samples were continuously exposed at 120 ° C., the control group was continuously deteriorated by heat to decrease the fluorescence intensity, whereas the fluorescent dye siloxane hybrid resin showed little change in fluorescence characteristics for 600 hours.

Table 2 compares the stability of the association of the fluorescent dye siloxane hybrid sample according to Example 4 with the concentration of the fluorescent dye of the control group. The control group is a sample obtained by simply mixing a fluorescent dye having the same concentration as the fluorescent dye siloxane hybrid resin with the siloxane resin and curing. As the concentration of the fluorescent dye increases from 0.1mM to 3mM, the fluorescence intensity continuously increases in the case of the fluorescent dye siloxane hybrid resin, whereas the control group decreases the fluorescence intensity as the concentration of the fluorescent dye increases. This control can be confirmed that the fluorescence intensity is reduced due to the association of the fluorescent pigment at high concentration, but the fluorescent pigment siloxane hybrid resin is not associated by the hybrid. From the above, it can be seen that the fluorescent dye siloxane hybrid resin according to the present invention is prevented from the association of the fluorescent dyes generally shown in the prior art and has excellent thermal stability, light stability, and fluorescence properties.

Claims (19)

Isocyanate group to which fluorescent dyes are bonded, including one or two or more functional groups selected from hydroxyl group, carboxyl group, urethane group, urea group, primary amino group, secondary amino group, tertiary amino group, cyano group and isothiocyanate group And an alkoxysilane comprising at least one functional group selected from isothiocyanate group, (C1-C20) alkoxy group, hydroxy group, epoxy group, halide group, carbonyl group, amino group and alken group Fluorescent dye siloxane hybrid resin prepared by non-aqueous condensation reaction of the organoalkoxysilane mixture represented by the structure of the formula (7):
[Chemical Formula 6]

(7)

In Chemical Formula 6, R ₇ is (C 1 -C 20) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 8) alkyl substituted with (C 3 -C 8) cycloalkyl, (C 2 -C 20) alkenyl, (C 2 -C20) alkynyl, (C6 ~ C20) aryl, wherein R ₇ may have one or more functional groups selected from acryl, methacryl, vinyl, and epoxy groups;
R ₂ is linear or branched (C 1 -C 7) alkyl;
In Formula 7, R ₈ and R ₉ are independently (C 1 -C 20) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 8) cycloalkyl substituted with (C 1 -C 20) alkyl, (C 2 -C 20) Alkenyl, (C2-C20) alkynyl, (C6-C20) aryl;
R ₈ and R ₉ are an acryl group, methacryl group, allyl group, halogen group, amino group, mercapto group, ether group, ester group, (C1-C20) alkoxy group, sulfone group, nitro group, hydroxy group, cyclo It may have one or more functional groups selected from butene groups, carbonyl groups, carboxyl groups, alkyd groups, urethane groups, vinyl groups, nitrile groups, and epoxy groups.
The method of claim 1,
The alkoxysilane to which the fluorescent dye is bonded is a fluorescent dye siloxane hybrid resin prepared by reacting a fluorescent dye including a hydroxyl group with a compound of Formula 1 or a mixture thereof:
[Formula 1]

In Formula 1, R ₁ is (C ₁ -C 20) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 8) alkyl substituted with (C 3 -C 8) cycloalkyl, (C 2 -C 20) alkenyl, (C 2- C20) alkynyl, (C6-C20) aryl, wherein R ₁ may have one or more functional groups selected from isocyanates, (C1-C20) alkoxy groups, hydroxy groups;
R ₂ is linear or branched (C 1 -C 7) alkyl.
The method of claim 1,
The fluorescent dye-bonded alkoxysilane is a fluorescent dye siloxane hybrid resin prepared by reacting a fluorescent dye comprising at least one of a carboxyl group, a urethane group, and a urea group with a compound of Formula 2 or a mixture thereof:
(2)

In Formula 2, R ₃ is (C 1 -C 20) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 8) cycloalkyl substituted with (C 4 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 2- C20) alkynyl, (C6 ~ C20) aryl, wherein R ₃ has an isocyanate functional group;
R ₂ is linear or branched (C 1 -C 7) alkyl.
The method of claim 1,
The fluorescent dye-bonded alkoxysilane is a fluorescent dye siloxane hybrid resin prepared by reacting a fluorescent dye comprising one or more selected from primary, secondary, and tertiary amino groups with a compound of Formula 3 or a mixture thereof. :
(3)

In Formula 3, R ₄ is (C 1 -C 20) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 8) alkyl substituted with (C 3 -C 8) cycloalkyl, (C 2 -C 20) alkenyl, (C 2- C20) alkynyl, (C6-C20) aryl and R ₄ may have one or more functional groups selected from isocyanate groups, isothiocyanate groups, epoxy groups, halide groups, carbonyl groups;
R ₂ is linear or branched (C 1 -C 7) alkyl.
The method of claim 1,
The alkoxysilane to which the fluorescent dye is bonded is a fluorescent dye siloxane hybrid resin prepared by reacting a fluorescent dye including a cyano group with a compound of Formula 4 or a mixture thereof:
[Chemical Formula 4]

In Formula 4, R ₅ is (C 1 -C 20) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 8) alkyl substituted with (C 3 -C 8) cycloalkyl, (C 2 -C 20) alkenyl, (C 2- C20) alkynyl, (C6-C20) aryl and R ₅ may have one or more functional groups selected from amino, alkene, and halide groups;
R ₂ is linear or branched (C 1 -C 7) alkyl.
The method of claim 1,
The fluorescent dye-bonded alkoxysilane is a fluorescent dye siloxane hybrid resin prepared by reacting a fluorescent dye including isothiocyanate with a compound of Formula 5 or a mixture thereof:
[Chemical Formula 5]

In Chemical Formula 5, R ₆ is (C 1 -C 20) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 8) alkyl substituted with (C 3 -C 8) cycloalkyl, (C 2 -C 20) alkenyl, (C 2- C20) alkynyl, (C6 ~ C20) is selected from aryl, wherein R ₆ has an amino functional group;
R ₂ is linear or branched (C 1 -C 7) alkyl.
delete The method of claim 1,
The fluorescent dyes are Rhodamine, Coumarin, Fluorescein, Perylene, 4-Dicyanomethylene-2-methyl-6-p-dimethylaminostyryl-4H-pyran (4-dicyanomethylene-2-methyl-6-p-dimethylaminostyryl-4H-pyran: DCM) and a fluorescent dye siloxane hybrid resin having at least one structure selected from pyrazine as a parent.
delete The method of claim 1,
The organoalkoxysilane is 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltrie Methoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltripropoxysilane , 3-acryloxypropylmethylbis (trimethoxy) silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3- (meth) Acryloxypropyl trimethoxysilane, 3- (meth) acryloxypropyl triethoxysilane, 3- (meth) acryloxypropyl tripro Fluorosilane hybrid siloxane resin selected from a foxysilane, or a mixture thereof.
delete The method of claim 1,
Wherein said organosilanediol is selected from diphenylsilanediol, diisobutylsilanediol or mixtures thereof.
The method of claim 1,
The condensation reaction is a fluorescent dye siloxane hybrid resin is a non-aqueous sol-gel reaction.
The method of claim 1,
The fluorescent dye siloxane hybrid includes any one or two or more heat-curable or UV-curable functional groups selected from an epoxy group, an acryl group, a methacryl group, a vinyl group, an amino group, and a hydroxy group in the organic group of the organoalkoxysilane or organosilanediol. Fluorescent dye siloxane hybrid resin, characterized in that.
The method of claim 1,
Fluorescent dye siloxane hybrid resin, characterized in that it comprises a curing agent for thermosetting or ultraviolet curing in the fluorescent dye siloxane hybrid.
The method of claim 1,
The fluorescent dye siloxane hybrid further comprises a fluorescent dye siloxane comprising any one or two or more photocurable or thermosetting functional monomers selected from an epoxy group, an acrylic group, a methacryl group, a vinyl group, an amino group and a hydroxy group. Hybrid resin.
The method of claim 1,
Fluorinated siloxane hybrid resin, characterized in that it comprises an addition reaction regulator and a solvent in order to impart curability to the fluorescent dye siloxane hybrid and control the viscosity.
The method of claim 1,
The fluorescent dye siloxane hybrid includes at least one selected from the group consisting of quantum dots, inorganic phosphors, conjugated polymers, surfactants, antioxidants, active oxygen scavengers, silica sol, oxide or nitride nanoparticles, flame retardants, metal fillers and heat resistant agents. Fluorescent dye siloxane hybrid resin, characterized in that.
An optical wavelength converter, a laser, a color filter, a solar cell or an LED element in which the fluorescent dye siloxane hybrid resin according to any one of claims 1 to 6, 8, 10 and 12 to 18 is used.